KR101898289B1 - Method for reducing organic acid in a hydrocarbon oil - Google Patents
Method for reducing organic acid in a hydrocarbon oilDownload PDFInfo
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- KR101898289B1 KR101898289B1KR1020120000367AKR20120000367AKR101898289B1KR 101898289 B1KR101898289 B1KR 101898289B1KR 1020120000367 AKR1020120000367 AKR 1020120000367AKR 20120000367 AKR20120000367 AKR 20120000367AKR 101898289 B1KR101898289 B1KR 101898289B1
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- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
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- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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- C10G2300/201—Impurities
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Abstract
Translated fromKoreanDescription
Translated fromKorean본 발명은 탄화수소류 유분, 보다 구체적으로는 미정제 원유 또는 상압 잔사유 등의 탄화수소류 유분 중의 유기산을 탄화수소류로 전환시켜 유기산을 저감하는 방법에 관한 것이다.The present invention relates to a method for reducing an organic acid by converting an organic acid in a hydrocarbon oil fraction, more specifically, a hydrocarbon oil fraction such as crude oil or atmospheric residue, into a hydrocarbon.
원유 내에는 다양한 종류의 이물질이 존재하는데, 이 중 유기산은 원유 처리 공정에 강한 부식 작용을 나타내는 대표적인 물질이다. 유기산의 함량은 전산가(Total Acid Number, mg KOH/g)로 나타내는데, 전산가는 시료 1g에 포함된 산을 적정하는데 소모되는 KOH의 질량(mg)으로서, 일반적으로 전산가가 0.5mg/KOH을 초과하는 원유는 고산도원유로 분류한다.There are various kinds of foreign materials in crude oil, among which organic acids are a typical material exhibiting a strong corrosive action in crude oil processing. The content of organic acid is expressed by Total Acid Number (mg KOH / g), which is the mass (mg) of KOH consumed to titrate the acid contained in 1 g of the sample. Generally, the total acid value exceeds 0.5 mg / KOH Crude oil is also classified as high mountain crude oil.
고산도원유는 주로 서아프리카, 북해, 중국, 남미 지역에서 생산되고 있다. 과거 저유가 시대에는 고산도원유가 개발되지 않았지만 유가가 상승하고 채산성이 확보되면서 고산도원유의 생산량은 점차 증가하고 있는 추세이다. 특히 서아프리카와 남미가 고산도원유 생산량 증가를 주도하고 있다. 향후에도 고산도원유의 생산량은 점점 증가할 것으로 예상되고 있다.High-grade crude oil is mainly produced in West Africa, North Sea, China and South America. In the past, crude oil was not developed in the past, but oil prices have risen and profitability has been secured, and production of high-grade crude oil has been gradually increasing. In particular, West Africa and South America are leading the increase in crude oil production. In the future, production of high-grade crude oil is expected to increase gradually.
고산도원유는 대부분 중질(重質)하고 황 함량이 낮아 주로 발전용이나 선박용 연료로 처리된다. 그 결과 고산도원유의 경제성은 발전용, 선박용 연료의 시장상황에 좌우된다. 전세계적인 온실가스 감축 노력 및 원유 가격 상승으로 산업용, 발전용 연료 사용량은 감소할 것으로 전망되고, 대규모 원유 정제시설 신설로 인한 공급 증가가 수요증가를 초과하여 단순정제마진이 마이너스가 될 것으로 전망된다. 이러한 산업용, 발전용 연료 수요감소, 단순정제마진 감소로 고산도원유를 연료 생산용으로 처리하는 것은 경제성이 매우 낮아질 것으로 예상된다. 그러나, 저급의 중질유분을 양질의 경질유분으로 업그레이드하는 고도화 공정에 고산도원유를 처리할 경우, 그 경제성은 양호할 것으로 전망된다.High-grade crude oil is mostly heavy and has low sulfur content and is mainly treated for power generation or marine fuel. As a result, the economics of high-altitude crude oil depend on market conditions for power generation and marine fuel. Fuel consumption for industrial and power generation is expected to decline due to global efforts to reduce GHG emissions and rising crude oil prices, and simple refining margins are projected to be negative, as the supply increase due to the establishment of large-scale crude oil refining facilities will exceed demand growth. Due to the decrease in demand for industrial and power generation fuels and the decrease in simple refining margins, it will be very economical to treat high-grade crude oil for fuel production. However, when the high-grade crude oil is treated in the upgrading process to upgrade the low-grade heavy oil to the high-quality light oil, the economic efficiency is expected to be favorable.
고산도원유를 처리하는 전통적인 기술은 산도가 낮은 일반원유와 배합하는 기술, 부식방지제를 적용하여 처리하는 기술, 그리고 공정재질을 내부식 재질로 개선하는 방법들이 있다. 그러나 이러한 방법들은 정유공정에서 고산도원유를 제한적으로만 처리할 수 있고, 초기 투자 비용이 과다하게 드는 단점이 있다. 저가에 거래되는 고산도원유를 경제적으로 처리하여 고도화 공정에 투입할 수 있다면 경제성을 높일 수 있을 것이다.Traditional techniques for treating high-altitude crude oil include blending techniques with low-acidity crude oil, techniques for applying anti-corrosion agents, and methods for improving process materials to internal materials. However, these methods have the disadvantage that they can only deal with high-grade crude oil in the refinery process, and the initial investment cost is excessive. High-cost crude oil, which is traded at a low price, can be economically processed and put into the upgrading process.
미국 특허 제6054042호, 제6096196호는 여러 가지 중화제를 사용하여 고산도원유 내의 유기산을 중화하여 부식성을 저감시키는 방법을 제시하고 있다. 그런데 중화제를 사용할 경우 유기산과 중화제가 염을 형성하는데, 이 염이 계면활성제로 작용하여 탈염과정에서 에멀젼을 형성하게 된다. 에멀젼이 과다하게 생성될 경우 탈염장치(Desalter)에서 유수분리가 원활하게 일어나지 않게 되어, 물이 원유로 유입되어 후단 공정에서 문제를 일으킬 수 있다.U.S. Patent Nos. 6054042 and 6096196 disclose methods for neutralizing organic acids in high acidity crude oil using various neutralizing agents to reduce the corrosiveness. However, when a neutralizing agent is used, the organic acid and the neutralizing agent form a salt, which acts as a surfactant to form an emulsion in the desalting process. If the emulsion is excessively produced, the water separation in the desalter does not occur smoothly, and water may flow into the crude oil, which may cause problems in the post-processing.
미국특허 제5683626호, 제6258258호, 및 유럽특허 제092428호에서는 암모늄 하이드록사이드, 암모니아, 망간산화물을 이용하여 유기산을 에스터, 아마이드, 케톤의 형태로 바꾸어, 유기산의 부식성을 저감하는 방법을 제시하고 있다. 그러나 상기 반응 시간이 길어 실제 공정에 사용하기에는 현실적으로 어렵고, 반응 후 생성된 화합물이 안정하지 않아 다시 유기산으로 되돌아 갈 수 있어 상업적 적용에는 불리한 단점이 있다.U.S. Patent Nos. 5683626 and 6258258 and European Patent No. 092428 disclose a method of reducing the corrosiveness of organic acids by converting organic acids into ester, amide and ketone forms using ammonium hydroxide, ammonia, and manganese oxide . However, since the reaction time is long, it is practically difficult to use in an actual process, and after the reaction, the resulting compound is not stable and can be returned to the organic acid, which is disadvantageous for commercial application.
또한, 미국특허 제6086751호는 원유 또는 잔사유분을 350 내지 400℃의 고온에서 수십 분에서 수시간 동안 열처리하여 탄화수소류 유분의 전산가를 0.5 이하로 저감하는 방법을 제시하고 있는데, 여기서 불활성기체를 반응기에 주입하여 탈탄산반응으로 생성된 물, 일산화탄소, 이산화탄소 등을 제거하여 전산가를 더 낮출 수 있다고 제시하고 있다. 그러나, 전산가 저감률을 높이기 위해서는 불활성기체를 주입하는 공정이 필요한 단점이 있다.In addition, U.S. Patent No. 6,086,751 discloses a method for reducing crude oil or residue oil at a high temperature of 350 to 400 ° C for several tens of minutes to several hours to reduce the total amount of hydrocarbon oil fraction to 0.5 or less. To remove water, carbon monoxide, and carbon dioxide generated by the decarbonation reaction, thereby lowering the computation cost. However, there is a disadvantage in that a step of injecting an inert gas is required to increase the reduction rate of the computer.
미국특허 제20060016723A1호는 금속산화물을 촉매로 사용하는 유기산 탈탄산반응을 통해 부식성을 저감하는 방법을 제시하고 있다. 여기서 촉매로 제시한 금속산화물은 산화마그네슘, 산화칼슘 등인데, 이 중 산화마그네슘이 전산가 저감률이나 장기 안정성 측면에서 우수하다고 설명하고 있다. 그러나, 실질적으로는 산화마그네슘 사용시 전산가 저감률이 낮고, 촉매 활성이 장기간 지속되지 못하는 단점이 있다.U.S. Patent No. 20060016723A1 discloses a method of reducing corrosivity through organic acid decarboxylation using a metal oxide as a catalyst. Here, the metal oxide suggested as a catalyst is magnesium oxide, calcium oxide, and the like, and it is explained that magnesium oxide is excellent in terms of reduction in computation cost and long-term stability. However, practically, when magnesium oxide is used, there is a disadvantage in that the reduction rate of computation cost is low and the catalytic activity can not be maintained for a long period of time.
미국특허 제6063266호는 상용 수첨처리 촉매를 사용하고 100 내지 300℃의 온도, 1 내지 50bar의 압력 조건, 바람직하기는 200 내지 250℃의 온도, 20 내지 30bar의 압력 조건에서 고산도원유를 처리하여 유기산 탈탄산반응을 통해 전산가를 저감시키는 방법을 제시하고 있다. 이 방법은 전산가 저감률이 높은 장점이 있으나, 반응기뿐만 아니라 여러 개의 세퍼레이터, 스트리퍼 등의 부수 공정을 설치해야 하고, 실질적으로 20bar 이상의 높은 압력 하에서 실시되어야 하므로 상압증류탑 전단에 반응기를 설치할 경우 반응기 시스템 압력을 조절하는데 어려움이 있을 수 있다.U.S. Patent No. 6,063,266 discloses a process for the treatment of high acidity crude oil using a commercial hydrotreating catalyst and at a temperature of 100 to 300 ° C, a pressure of 1 to 50 bar, preferably 200 to 250 ° C, and a pressure of 20 to 30 bar And suggests a method of reducing the computation cost through organic acid decarboxylation. This method is advantageous in that the reduction rate of computation is high. However, it is necessary to install additional process such as separator, stripper, etc. in addition to the reactor. Therefore, when the reactor is installed on the upstream side of the atmospheric distillation column, May be difficult to control.
따라서, 원유 또는 이의 분획으로부터 부식의 원인이 되는 유기산을 정제기 상에서 제거하거나, 실질적으로 저감시키기 위한 보다 효율적이고 경제적인 방법에 대한 필요가 여전히 남아 있다.Thus, there remains a need for a more efficient and economical process for removing or substantially reducing the organic acids that cause corrosion from crude oil or fractions thereof on the purifier.
본 발명자들은 탄화수소류 유분 내의 유기산을 저감하는 방법으로서, 적절한 조건 하에서 수소 또는 수소 함유 가스와 촉매를 사용한 유기산의 탈탄산 반응에 의하여 탄화수소류 유분 내의 유기산을 저감하는 방법을 도출하였다.The present inventors have developed a method for reducing organic acids in hydrocarbon oil fractions by decarboxylation of organic acids using hydrogen or a hydrogen-containing gas and a catalyst under appropriate conditions as a method for reducing organic acids in hydrocarbon oil fractions.
따라서, 본 발명은 원유 처리 공정에서 부식을 일으키는 주원인인 나프텐산(Naphthenic Acid)과 같은 유기산을 효과적으로 제거하는 새로운 방법을 제공한다.Accordingly, the present invention provides a novel method for effectively removing organic acids such as naphthenic acid, which is the main cause of corrosion in crude oil processing.
본 발명은 탄화수소류 유분 내의 유기산을 저감하는 방법으로서, 이 방법은 수소화 촉매의 존재에서, 약 300℃ 내지 400℃의 온도 및 약 3 내지 15kg·f/㎠의 압력 하에서 약 1 내지 100의 H2/유분(Oil)의 비로 수소 가스 또는 수소 혼합가스를 공급하여 탄화수소류 유분을 수소화하는 단계를 포함한다. 상기 탄화수소류 유분은 고산도 원유 또는 원유 분획일 수 있다.The present invention provides a method for reducing organic acids in the hydrocarbon oil, the method in the presence of a hydrogenation catalyst, under a pressure of temperature and about 3 to 15kg · f / ㎠ of about 300 ℃ to 400 ℃ of from about 1 to 100 H2 / Oil to hydrogen gas or hydrogen mixture gas to hydrogenate the hydrocarbon oil fraction. The hydrocarbon fraction may be a high acidity crude oil or a crude oil fraction.
본 발명에 따르면, 하기 화학식과 같은 기전(Mechanism)에 따라 나프텐산과 같은 유기산이 탈탄산 반응을 거쳐 탄화수소류로 전환된 결과 유분 처리 공정 시 부식의 원인이 되는 유기산을 저감시킬 수 있다.According to the present invention, organic acids such as naphthenic acid are converted to hydrocarbons through a decarboxylation reaction according to the mechanism as shown below to reduce organic acids which cause corrosion in the oil treatment process.
본 발명에 따르면, 비교적 낮은 압력의 마일드한 조건 하에서 원유 처리 공정시 부식을 일으키는 유기산을 효과적으로 제거할 수 있는 유기산 저감 방법을 제공한다.According to the present invention, there is provided an organic acid abatement method capable of effectively removing organic acids that cause corrosion in a crude oil treatment process under mild conditions of relatively low pressure.
특히, 본 발명은 상압증류공정의 전 또는 후 단계에 각각 적용될 수 있는 적절한 수소화 공정 조건을 제시함으로써 고산도 원유 또는 이의 분획의 효율적인 유기산 저감 방법을 제공한다.In particular, the present invention provides an efficient method for reducing organic acids in high-acid crude oil or its fractions by suggesting suitable hydrogenation process conditions that may be applied respectively before or after the atmospheric distillation process.
도 1은 상압증류 공정 전단에 반응기를 배치하여 미정제 원유를 수소화하는 본 발명의 일 구체예의 개략적인 흐름도이다.
도 2는 원유 증류 후 얻어진 상압 잔사유를 수소화하는 본 발명의 다른 구체예의 개략적인 흐름도이다.1 is a schematic flow diagram of one embodiment of the present invention in which a reactor is placed upstream of an atmospheric distillation process to hydrogenate crude crude.
2 is a schematic flow diagram of another embodiment of the present invention for hydrogenating atmospheric residuum obtained after crude oil distillation.
본 명세서에서, "탄화수소류 유분"이라는 용어는 미정제 원유, 원유의 분획, 상압증류 공정에 의한 원유 정제 후 얻어진 상압 잔사유, 고도화 공정 유분(고도화 정제 공정 후 얻어진 유분 분획), 바이오 연료 등을 광범위하게 포함하는 임의의 유분을 지칭하는 것으로 해석된다. 본 명세서에서, "유기산"이라는 용어는 탄화수소류 유분 처리 공정에서 강한 부식 작용을 나타내는 임의의 유기산을 지칭하는 것으로 해석된다. 예를 들면, 나프텐기 또는 파라핀기를 포함하는 유기산, 주로 나프텐기를 포함하는 나프텐산(Naphthenic acid)을 포함한다.As used herein, the term "hydrocarbon oil fraction" refers to crude oil, fraction of crude oil, atmospheric residues obtained after crude oil purification by atmospheric distillation process, upgraded oil fraction (oil fraction obtained after advanced refining process) Is interpreted to refer to any oil that is broadly included. As used herein, the term "organic acid" is interpreted to refer to any organic acid that exhibits a strong erosive action in a hydrocarbon oil treatment process. For example, naphthenic acid or an organic acid including a paraffinic group, and naphthenic acid mainly containing a naphthenic group.
탄화수소류 유분 내의 유기산 함량은 일반적으로 전산가(Total Acid Number, mg KOH/g)로 나타내는데, 전산가는 시료 1g에 포함된 산을 적정하는데 소모되는 KOH의 질량(mg)이다. 일반적으로 전산가가 0.5mg/KOH을 초과하는 원유는 고산도 원유로 분류되므로, 본 발명의 한 구체예에서는 전산가가 약 0.5mg/KOH을 초과하는 고산도 탄화수소류 유분을 처리 대상으로 할 수 있다.The organic acid content in the hydrocarbon oil fraction is generally expressed as a total acid number (mg KOH / g), which is the mass (mg) of KOH consumed for titrating the acid contained in 1 g of the sample. Generally, crude oil having an acid value of more than 0.5 mg / KOH is classified as a high acidity crude oil. Therefore, in one embodiment of the present invention, a high acidity hydrocarbon oil fraction having an acid value of more than about 0.5 mg / KOH can be treated.
유기산은 통상적으로 저온에서는 부식이 일어나지 않으나, 230℃ 이상의 고온에서는 매우 강한 부식 활성을 나타내는 것으로 알려져 있다. 유기산은 금속물질과 결합하여 금속염을 생성하는데 이러한 금속염은 파울링(Fouling)과 같은 공정문제의 원인물질이다. 더불어 유기산은 원유 탈염과정에서 물과 결합하여 안정한 에멀젼을 형성하여 탈염효율을 저하시키기도 하므로 제거되어야 한다Organic acids generally do not cause corrosion at low temperatures, but are known to exhibit very strong corrosion activity at high temperatures above 230 ° C. Organic acids combine with metal materials to form metal salts, which are the cause of process problems such as fouling. In addition, organic acids should be removed because they combine with water in the crude oil desalination process to form a stable emulsion which lowers the desalination efficiency
본 명세서에서 사용되는 "수소화 촉매"란, 탄화수소류 유분 내에 존재하는 유기산의 탈탄산 반응, 예를 들면 다음과 같은 기전을 통한 탈탄산 반응을 촉진하여, 탄화수소류와 이산화탄소, 일산화탄소, 수증기 등의 오프 가스(Off Gas)를 발생시킬 수 있는 상용 촉매를 지칭하는 것으로 해석된다.As used herein, the term "hydrogenation catalyst" means a deacidification reaction of an organic acid present in a hydrocarbon oil fraction, for example, a decarboxylation reaction through a mechanism such as the following, thereby reducing off hydrocarbons and carbon dioxide, carbon monoxide, Is meant to refer to a commercial catalyst capable of generating off gas.
본 발명에서 사용되는 수소화 촉매로는 상용화된 수첨 처리 촉매, 탈황 촉매 등을 들 수 있다. 보다 구체적으로, 가스 오일 (Gas Oil) 수첨 탈황 촉매(예: 알루미나에 코발트(Co) 및 몰리브덴(Mo)이 담지된 촉매), 상압 잔사유 또는 감압 잔사유 탈황공정에 사용되는 중금속 흡착 촉매(예: 알루미나에 니켈(Ni) 및 몰리브덴(Mo)이 담지된 중금속 흡착촉매), 수첨처리(탈황, 탈질) 촉매(예: 알루미나에 니켈(Ni) 및 몰리브덴(Mo)이 담지된 수첨 탈황 촉매), 또는 이들 촉매들의 기능들을 혼합한 촉매일 수 있으나 이들로 제한되는 것은 아니다. 본 발명에 따른 수소화 촉매는 새 촉매일 수 있으나, 경제성을 높이기 위하여 폐촉매를 사용할 수도 있다.Examples of the hydrogenation catalyst used in the present invention include commercially available hydrogenation catalysts and desulfurization catalysts. More specifically, a gas oil hydrodesulfurization catalyst (for example, a catalyst in which cobalt (Co) and molybdenum (Mo) are supported on alumina), a heavy metal residue adsorbing catalyst (A heavy metal adsorption catalyst in which nickel (Ni) and molybdenum (Mo) are supported on alumina), a hydrogenation catalyst (such as a desulfurization and denitration catalyst) Or catalysts that combine the functions of these catalysts. The hydrogenation catalyst according to the present invention may be a new catalyst, but a spent catalyst may be used to improve the economical efficiency.
수소화 공정에서, 반응온도가 증가할수록 유기산 저감율은 선형으로 증가한다. 즉, 이론적으로는 반응온도가 높을수록 유기산 저감율이 상승하지만, 반응온도가 높은 경우에는 높은 반응온도를 유지하기 위한 운전 비용이 상승한다는 문제점이 있다. 또한, 반응온도에 맞는 적절한 반응압력의 제어가 촉매 비활성화 방지를 위하여 필요하다.In the hydrogenation process, as the reaction temperature increases, the organic acid reduction rate increases linearly. That is, theoretically, the higher the reaction temperature, the higher the organic acid reduction rate, but the higher the reaction temperature, the higher the operation cost for maintaining the higher reaction temperature. In addition, control of the reaction pressure appropriate for the reaction temperature is necessary for preventing the catalyst deactivation.
따라서, 본 발명에 따른 수소화 공정은 약 300℃ 내지 400℃의 온도 및 약 3 내지 15kg·f/㎠의 압력 하에서 실시되는 것이 바람직하다. 더욱 바람직하기는, 수소화 공정 중 온도는 반응기의 온도를 높이기 위한 추가 에너지 공급이 필요없는, 상압증류탑 전의 히터 후단 온도 또는 상압증류탑 후단의 온도범위인 것이다.Therefore, the hydrogenation process according to the present invention is preferably carried out at a temperature of about 300 ° C to 400 ° C and a pressure of about 3 to 15 kg · f / cm 2. More preferably, the temperature during the hydrogenation process is the temperature at the rear end of the heater before the atmospheric distillation column or the temperature at the rear end of the atmospheric distillation column, which does not require additional energy supply for raising the temperature of the reactor.
본 발명의 한 구체예에서 탄화수소류 유분은 수소화 처리 전 임의로 물과 혼합하여 탈염화 공정을 거친 미정제 원유일 수 있다. 예를 들면, 미정제 원유는 약 300℃ 내지 400℃의 온도 및 약 3 내지 10kg·f/㎠의 압력 하의 수첨 처리 촉매 존재 하에서 약 1 내지 100의 H2/유분(Oil)의 부피비(1 내지 100NL H2/유분(L))로 수소 가스를 공급하여 수소화할 수 있다. 수소화 공정 처리 후 미정제 원유는 상압증류 정제 공정을 거칠 수 있다.In one embodiment of the present invention, the hydrocarbon oil fraction may be crude and unrefined after it has been subjected to a dechlorination process, optionally before mixing with water, prior to hydrotreating. For example, the crude oil may have a volume ratio (1 to 100) of H2 / oil of about 1 to 100 in the presence of a hydrotreating catalyst at a temperature of about 300 ° C to 400 ° C and a pressure of about 3 to 10 kgf / 100 NL H2 / oil (L)). After the hydrotreating process, crude crude may be subjected to an atmospheric distillation purification process.
본 발명의 다른 구체예에서는, 탄화수소류 유분이 상압증류 공정에 의한 원유 정제 후의 잔사유이고, 약 300℃ 내지 400℃의 온도 및 약 10 내지 15kg·f/㎠의 압력 하의 탈황 촉매 존재 하에서 약 1 내지 100의 H2/유분의 부피비로 수소 가스를 공급하여 상압 잔사유를 수소화할 수 있다.In another embodiment of the present invention, the hydrocarbon oil fraction is residual oil after crude oil purification by an atmospheric distillation step, and is characterized in that the hydrocarbon oil fraction is residual oil after crude oil purification at a temperature of about 300 ° C to 400 ° C and in the presence of a desulfurization catalyst at a pressure of about 10 to 15 kgf / Hydrogen gas may be supplied at a ratio of H2 / oil fraction of 100 to 100 to thereby hydrogenate the atmospheric residue oil.
본 발명에 따른 수소화 단계에서, 수소화 공정에 도입되는 H2/유분의 부피비는 약 1 내지 100, 보다 구체적으로는 약 1 내지 10, 보다 더 구체적으로는 약 1 내지 5이다. H2/유분의 비가 높을 경우 운전 비용을 상승시키고, 오프-가스 분리에 어려움을 일으키는 반면, 너무 적은 양의 수소가 주입되는 경우에는 촉매의 비활성화를 야기시키는 문제점이 있다. 따라서, 본 발명의 구체예에서는 바람직한 유기산 저감율(약 70% 이상)을 얻을 수 있는 H2/유분 비의 범위 내에서 가능한한 적은 양의 수소 가스를 주입하는 것이 바람직하다.In the hydrogenation step according to the invention, the volume ratio of H2 / oil introduced into the hydrogenation process is from about 1 to 100, more specifically from about 1 to 10, more particularly from about 1 to 5. When the ratio of H2 / oil is high, the operation cost is increased and the off-gas separation is difficult. On the other hand, when too little hydrogen is injected, the catalyst is inactivated. Therefore, in the embodiment of the present invention, it is preferable to inject as little hydrogen gas as possible within a range of H2 / oil fraction which can obtain a desirable organic acid reduction ratio (about 70% or more).
탄화수소류 유분의 종류에 따라 다소 차이가 있지만, 대부분의 탄화수소류 유분의 경우 유분 내 유기산의 저감율이 약 70% 이상인 경우, 유기산에 의한 부식 효과 등에 실질적인 차이가 없으므로, 유기산 저감율은 약 70% 이상인 것이 바람직하다.There is no substantial difference in the corrosion efficiency due to the organic acid when the reduction ratio of the organic acid in the oil is about 70% or more in the case of most of the hydrocarbon oils, so that the reduction ratio of the organic acid is about 70% or more desirable.
또한, 본 발명에 따른 수소화 공정에 사용되는 수소 가스는 순수한 수소 가스, 또는 수소 혼합 가스, 예를 수소화 공정을 거쳐 나온 혼합 가스일 수 있다. 혼합 가스는 약 5 내지 95중량%, 구체적으로 약 20 내지 80중량%의 수소를 포함하는 혼합 가스일 수 있으며, 본 발명에 따라 수소화 공정을 거쳐 나온 혼합 가스를 재사용할 경우 공정의 효율성 및 경제성을 높일 수 있다.In addition, the hydrogen gas used in the hydrogenation process according to the present invention may be a pure hydrogen gas or a hydrogen mixed gas, for example, a mixed gas obtained through a hydrogenation process. The mixed gas may be a mixed gas containing about 5 to 95% by weight, specifically about 20 to 80% by weight of hydrogen. When the mixed gas that has passed through the hydrogenation process according to the present invention is reused, the efficiency and economical efficiency of the process .
본 발명의 한 구체예에서, 수소화 단계 동안 탄화수소류 유분은 시간 당 약 1 내지 5의 LHSV(liquid hourly space velocity), 보다 구체적으로 시간 당 약 1 내지 3, 보다 더 구체적으로는 시간 당 약 1 내지 2의 LHSV로 공급될 수 있다.In one embodiment of the present invention, the hydrocarbon stream fraction during the hydrogenation step is maintained at a liquid hourly space velocity (LHSV) of about 1 to 5, more specifically about 1 to 3, more specifically about 1 to about 3, 2 LHSV. ≪ / RTI >
일반적으로 공간속도가 증가할수록 유기산 저감률은 선형적으로 감소하게 된다. 공간속도가 지나치게 높을 경우 촉매 가혹도 증가로 인해, 촉매 비활성화가 유도되어 촉매의 장기운전 성능에 악영향을 미치게 한다는 문제점이 있다. 반면, 공간속도가 너무 낮을 경우, 탄화수소류 유분 처리량이 적어진다는 문제가 있다. 따라서, 공정조건과 운전환경에 따라 공간속도를 상기한 범위 내에서 적절히 조절하는 것이 바람직하다.Generally, as the space velocity increases, the organic acid reduction rate decreases linearly. If the space velocity is excessively high, catalyst deactivation is induced due to increase in catalyst severity, which adversely affects the long-term operation performance of the catalyst. On the other hand, when the space velocity is too low, there is a problem that the amount of hydrocarbon oil processing is reduced. Therefore, it is preferable to appropriately adjust the space velocity within the above range according to the process conditions and the operating environment.
반응 시간은 처리될 탄화수소류 유분의 온도 및 특성, 산 함량 등에 따라 달라질 수 있으며, 이는 당업자에 의해 용이하게 결정될 수 있다.The reaction time may vary depending on the temperature and characteristics of the hydrocarbon fractions to be treated, the acid content, and the like, which can be easily determined by those skilled in the art.
본 발명에 따르면, 상기한 바와 같은 공정 변수의 조합에 의하여 탄화수소류 유분 중 황 화합물과 질소 화합물의 수소화는 실질적으로 거의 일어나지 않고, 유기산의 선택적인 탈산반응이 가능하므로 고가의 수소 소비량을 줄일 수 있다.According to the present invention, hydrogenation of the sulfur compound and the nitrogen compound in the hydrocarbon oil fraction is hardly caused by the combination of the process variables as described above, and the selective deoxidation reaction of the organic acid is possible, so that the high hydrogen consumption can be reduced .
한편, 본 발명의 한 구체예에서는 보다 경제적인 고산도 탄화수소류 유분의 유기산 저감 방법을 제공한다. 처리 공정의 경제성을 높이기 위한 방법으로는, 예를 들면 (i) 수소 주입량의 최소화, (ii) 혼합가스 사용, (iii) 폐촉매 사용을 들 수 있다.On the other hand, one embodiment of the present invention provides a more economical method for reducing organic acid in high acidity hydrocarbon oil fractions. As a method for improving the economical efficiency of the treatment process, for example, (i) minimization of hydrogen injection amount, (ii) use of mixed gas, and (iii) use of spent catalyst.
우선, 고산도 유분을 처리하기 위해서 수소의 주입은 필수적이지만, 과도한 수소의 주입은 운전 비용의 상승을 야기시키고 과도한 오프-가스를 생성한다는 문제점이 있기 때문에 유기산의 제거가 가능한 최소 수준, 예를 들면, 1 내지 100 NL H2/유분(L)의 비로 수소를 주입할 필요가 있다. 이때, 실제 주입되는 수소 가스 함량은 유분 대비 수소 가스 부피의 약 1 내지 10배 정도인 것이 바람직하고, 보다 바람직하게는 약 1 내지 5배인 것이다.First, the injection of hydrogen is necessary to treat high-acidity oil. However, since excessive hydrogen injection raises the operation cost and generates excessive off-gas, the minimum level of removal of organic acid is required, for example, , And 1 to 100 NL H2 / oil (L). At this time, the amount of hydrogen gas actually injected is preferably about 1 to 10 times, more preferably about 1 to 5 times, the volume of hydrogen gas relative to the oil.
또한, 본 발명에 따른 수소화 공정에서 순수한 수소 가스 이외에도, 휘발유, 경유 탈황 공정에서 발생하는, 수소 혼합 오프-가스를 수소 가스 공급원으로 사용할 수 있다. 수소 혼합 가스 사용시에는 오프-가스에 남아 있는 불순물 등이 촉매에 미치는 영향을 파악하여 적절한 오프-가스를 선별하여 사용하는 것이 바람직하다. 한편, 정유 공정에 사용되고 있는 촉매 중 활성이 남아있는 폐촉매를 이용할 경우 고산도 탄화수소류 유분 처리 공정의 경제성을 높일 수 있다. 반응의 한 구체예로서, 폐촉매를 활용한 파일럿 시험(Pilot Test) 결과, 새촉매와 폐촉매의 유기산 저감률은 유사한 수준인 것으로 나타났다(실시예 참조).In addition to the pure hydrogen gas in the hydrogenation process according to the present invention, a hydrogen mixing off-gas generated in a gasoline or gas-oil desulfurization process can be used as a hydrogen gas supply source. It is preferable to select and use an appropriate off-gas while grasping the influence of the impurities remaining in the off-gas on the catalyst when the hydrogen mixed gas is used. On the other hand, when the spent catalyst having activity remains in the catalyst used in the refining process, it is possible to increase the economical efficiency of the process of treating the high acidity hydrocarbon oil. As a result of the pilot test using the spent catalyst, the organic acid reduction ratio of the new catalyst and the spent catalyst was found to be similar (see Examples).
본 발명에 따른 탄화수소류 유분의 유기산 저감용 수소화 공정은 도 1 및 도 2에 도시된 바와 같이, 상압증류 공정 전 또는 후에 실시될 수 있다.The hydrogenation process for reducing the organic acid of the hydrocarbon oil fraction according to the present invention may be carried out before or after the atmospheric distillation process, as shown in FIG. 1 and FIG.
도 1을 참고하여 본 발명의 한 구체예를 설명하면, 고산도 탄화수소류 유분은 히터(Heater)로 도입되고 히터에서 상압증류탑 인렛(Inlet) 온도까지 가열된다. 가열된 탄화수소류 유분은 히터 후단에 설치된 유기산 저감용 수소화 반응기에 투입된다. 유기산 저감용 수소화 반응기에는 수소화 촉매가 충진되어 있으며 유기산 저감에 필요한 수소 가스가 연속적으로 공급되면서, 적정 반응 조건으로 유지된다. 반응기에서 나온 탄화수소류 유분은 상압증류탑으로 도입되어, 공정부식 없이 고도화 공정으로 처리가 가능하다.Referring to FIG. 1, a high acidity hydrocarbon fraction is introduced into a heater and heated from a heater to an atmospheric distillation column inlet temperature. The heated hydrocarbon fraction is fed to a hydrogenation reactor for reducing organic acids installed at the rear end of the heater. The hydrogenation reactor for organic acid reduction is filled with a hydrogenation catalyst, and hydrogen gas necessary for organic acid reduction is continuously supplied, and the reaction condition is maintained under proper conditions. The hydrocarbon fractions from the reactor are introduced into the atmospheric distillation column and can be treated in a high-grade process without process corrosion.
도 2를 참고하여 본 발명의 다른 구체예를 설명하면, 히터에서 가열된 고산도 탄화수소류 유분은 먼저 상압증류탑으로 도입되고, 상압 증류시 탄화수소류 유분의 유기산은 잔사유 내에 농축된다. 상압증류탑에서 나온 고산도 잔사유는 유기산 저감 반응에 충분한 온도를 지니며, 수소와 함께 촉매가 충진된 유기산 저감용 수소화 반응기로 도입된다. 반응기에서 유기산이 저감된 잔사유는 고도화 공정으로 유입된다.2, the high acidity hydrocarbon fraction heated in the heater is first introduced into the atmospheric distillation column, and the organic acid of the hydrocarbon fraction is concentrated in the residual oil during the normal pressure distillation. The high acid residue from the atmospheric distillation column has a sufficient temperature for the organic acid abatement reaction and is introduced into the hydrogenation reactor for the reduction of the organic acid with the catalyst filled with hydrogen. Residues with reduced organic acids in the reactor enter the upgrading process.
본 발명은 연속공정으로 이루어지며 상압증류탑 전의 히터 후단, 상압증류탑 후단에 반응기를 설치하여 별도의 에너지 추가 없이 운전이 가능하고, 폐촉매 및 수소 혼합가스의 사용으로 반응기만 설치하면 추가적인 공정 설비 없이도 운영이 가능하다는 장점이 있다. 또한, 고산도 탄화수소 유분류를 상압증류공정 단계에서 미리 처리함으로써 고도화 공정의 유기산으로 인하여 발생할 수 있는 부식 등 여러 제반 문제점들을 제거할 수 있다.The present invention has a continuous process and can be operated without additional energy by providing a reactor at the downstream end of the atmospheric distillation column and at the downstream end of the atmospheric distillation column. If only the reactor is installed by using the spent catalyst and the hydrogen mixed gas, Is possible. In addition, by treating the high acidity hydrocarbon oil classification beforehand in the step of the atmospheric distillation process, it is possible to eliminate various problems such as corrosion that may occur due to the organic acid in the upgrading process.
이하, 실시예에서 본 발명이 추가로 설명된다. 다만 본 실시예는 후술되는 청구범위에 정의된 발명의 범위를 제한하는 것으로 해석되어서는 안된다.
Hereinafter, the present invention will be further described in the examples. However, this embodiment should not be construed as limiting the scope of the invention as defined in the following claims.
실시예Example
실시예 1: 수소 가스에 의한 탄화수소류 유분 내의 유기산 저감Example 1: Reduction of organic acids in hydrocarbon oils by hydrogen gas
오토클레이브(Autoclave)를 이용하여 고산도 탄화수소 유분(Feed: 중국산 고산도 원유인 PENGLAI)과 유분 중량 기준으로 1wt%의 상압 잔사유 탈황공정에서 알루미나에 Ni 및 Mo이 담지된 수첨 탈황촉매를 주입한다. 고산도 탄화수소 유분의 총산가(TAN)는 약 2.0이다. 350℃에서 실험을 수행하고 반응기 내부의 고산도 탄화수소 유분과 촉매 혼합물은 메카니컬 교반기를 이용하여 교반속도 1000rpm으로 교반시킨다. 반응에 필요한 충분한 가스(수소, 질소)를 공급해 주기 위해서 가스는 반응기 내부에 초기 20kg·f/㎠를 충진하고 유기산 저감 반응 동안 반응기를 폐쇄 시스템(Close system)으로 유지한다. 총 5시간 반응시킨 후 냉각기(Coolant)를 이용해 최단시간에 반응기 온도를 상온으로 내린 다음 얻어진 유분(Product)의 TAN를 측정하였다(TAN 측정 방법: ASTM D664).The autoclave is used to feed a high-acid hydrocarbons feed (PENGLAI), which is a Chinese high-grade crude oil, and a hydrodesulfurization catalyst, in which Ni and Mo are supported on alumina in a 1 wt% atmospheric residue desulfurization process . The total acid value (TAN) of the aliphatic hydrocarbon oil is about 2.0. Experiments are carried out at 350 DEG C and the high acidity hydrocarbon oil and the catalyst mixture in the reactor are stirred at a stirring speed of 1000 rpm using a mechanical stirrer. In order to supply enough gas (hydrogen, nitrogen) necessary for the reaction, the gas is initially filled into the reactor at 20 kg · f / cm 2 and the reactor is maintained as a close system during the organic acid reduction reaction. After reacting for a total of 5 hours, the temperature of the reactor was lowered to room temperature in the shortest time using a coolant, and the TAN of the obtained product was measured (TAN measurement method: ASTM D664).
위의 실험에서 수소 대신 질소를 주입한 것을 제외하고는 다른 조건을 동일하게 하여 유기산 저감 반응을 진행하였다. 하기 표 1에 나타난 바와 같이, 수소 주입 경우의 유기산 저감률이 질소 주입의 경우보다 3배 이상 증가하였다.In the above experiment, organic acid abatement reaction was carried out under the same conditions except that nitrogen was injected instead of hydrogen. As shown in the following Table 1, the organic acid reduction rate when hydrogen was injected increased more than three times as compared with the case of nitrogen injection.
실시예 2: 반응 조건에 따른 탄화수소류 유분 내의 유기산 저감 효과Example 2: Reduction effect of organic acid in hydrocarbon fraction according to reaction conditions
연속 운전식 반응기에 상압잔사유용 상업 탈황 촉매 50 내지 100ml를 충진한다. 반응기는 360℃, 5kg·f/㎠ 조건을 유지하며 공급 탱크(Feed Tank)로부터 TAN 약 2인 고산도 탄화수소류 유분을 50 내지 200ml/hr(LHSV 1 내지 5hr-1)로 흘려주고 수소는 탄화수소류 유분 부피 대비 5 내지 25배로 연속적으로 반응기로 주입하여 반응시켰다.A continuous operation type reactor is charged with 50 to 100 ml of a commercial desulfurization catalyst useful for normal-pressure residues. The reactor was operated at a temperature of 360 ° C. and a pressure of 5 kg · f / cm 2, and a high-acid hydrocarbon fraction having a TAN of about 2 was fed from a feed tank at a rate of 50 to 200 ml / hr (LHSV 1 to 5 hr-1 ) And the mixture was continuously injected into the reactor at a rate of 5 to 25 times the volume of the oil fraction.
상기에서 설명한 연속 운전식 반응방법으로 고산도 탄화수소 유분의 반응 조건별 유기산 저감 효과를 확인하였다.
The effect of reducing the organic acid on the reaction conditions of the high acidity hydrocarbon oil was confirmed by the continuous operation type reaction method described above.
실시예 2-1: 반응 온도별 탄화수소류 유분 내의 유기산 저감Example 2-1: Reduction of organic acids in hydrocarbon oils by reaction temperature
상기 표 2에 나타난 바와 같이, 반응온도가 높아질수록 유기산 저감률이 증가한다는 것을 확인하였다.
As shown in Table 2, it was confirmed that the organic acid reduction rate increases as the reaction temperature increases.
실시예 2-2: 수소 주입량에 따른 탄화수소류 유분 내의 유기산 저감Example 2-2: Reduction of organic acids in hydrocarbon oils due to the amount of hydrogen injected
표 3에 나타난 바와 같이, 일정 범위의 수소 주입량 조건에서는 유기산 저감률이 높게 유지됨을 확인하였다.
As shown in Table 3, it was confirmed that the organic acid reduction rate was maintained at a high level under a certain hydrogen injection amount.
실시예 2-3: LHSV 별 탄화수소류 유분 내의 유기산 저감Example 2-3: Reduction of organic acids in hydrocarbons oil by LHSV
상기 표 4에서 보는 바와 같이, LHSV가 증가할수록 유기산 저감률은 감소한다는 것을 확인하였다.
As shown in Table 4, it was confirmed that the organic acid reduction rate decreases as the LHSV increases.
실시예 2-4: 혼합가스를 이용한 탄화수소류 유분 내의 유기산 저감Example 2-4: Reduction of organic acids in hydrocarbon oils using a mixed gas
연속 운전식 반응을 통해, 고순도 수소 대신에 수소와 질소를 혼합한 혼합가스를 사용하여 실험하였다. 그 결과, 표 5에 나타난 바와 같이, 혼합 가스 중 수소 함량이 50%인 경우에서도 유기산 저감률이 75% 이상이라는 것을 확인하였다.
Through a continuous operation reaction, a mixed gas of hydrogen and nitrogen was used instead of high purity hydrogen. As a result, as shown in Table 5, it was confirmed that the organic acid reduction rate was 75% or more even when the hydrogen content in the mixed gas was 50%.
실시예 3: 잔사유분 내의 유기산 저감Example 3 Reduction of Organic Acid in Residue Oil
연속 운전식 반응기에 상압 잔사유 탈황공정에서 알루미나에 Ni 및 Mo이 담지된 수첨 탈황촉매 50 내지 100ml를 충진한다. 반응기는 345℃, 12.5kg·f/㎠ 조건을 유지하며 공급 탱크(Feed Tank)로부터 TAN 약 4인 고산도 탄화수소류 유분(Feed: 아프리카산 고산도 원유인 Dar Blend의 상압 잔사유분)을 50 내지 100ml/hr(LHSV 1hr-1)로 흘려주고 수소는 탄화수소류 유분 부피 대비 5 내지 25배로 연속적으로 반응기로 주입하여 반응시켰다.In a continuous operation type reactor, 50 to 100 ml of a hydrodesulfurization catalyst in which Ni and Mo are supported on alumina is filled in an atmospheric residual gas desulfurization process. The reactor was maintained at 345 ° C and 12.5 kg · f / cm 2, and was fed with a TAN of about 4 from a feed tank at a feed rate of 50 to 100 kg / 100 ml / hr (LHSV1 hr-1 ), and hydrogen was continuously injected into the reactor at a rate of 5 to 25 times the volume of the hydrocarbon oil.
상기에서 설명한 연속 운전식 반응방법으로 고산도 탄화수소 유분의 반응 조건별 유기산 저감 효과를 확인하였다
The effect of reducing the organic acid by the reaction conditions of the high acidity hydrocarbon oil was confirmed by the continuous operation type reaction method described above
실시예 3-1: 수소 주입량에 따른 잔사유분 내의 유기산 저감Example 3-1: Reduction of organic acid in residues due to the amount of hydrogen injected
고산도 잔사유를 본 발명에 따른 일정 범위의 H2/유분 비로 수소 가스 처리하면, 잔사유 내의 유기산 저감률이 70% 이상이 될 수 있음을 확인하였다.
It was confirmed that the organic acid reduction ratio in residual oil can be 70% or more when the high acidity residues are subjected to hydrogen gas treatment with a certain range of H2 / oil ratio according to the present invention.
실시예 3-2: 폐촉매를 이용한 잔사유분 내의 유기산 저감Example 3-2: Reduction of organic acid in residue oil using spent catalyst
새촉매 또는 폐촉매(상압잔사유 탈황공정에서 11개월 간 사용된 알루미나에 Ni 및 Mo이 담지된 탈황촉매)를 사용하여 실시예 2와 동일한 연속 운전식 반응 조건 하에서 총산가가 4.2 mgKOH/g인 잔사유에 대한 유기산 저감 시험을 실시하였다. 표 7에 나타난 바와 같이, 폐촉매 사용시에도 새촉매와 비슷한 유기산 저감 성능을 얻을 수 있다는 것을 확인하였다. 따라서, 폐촉매의 유기산 저감 활성은 산업적으로 유기산 저감용으로 활용 가능한 수준이다.
Using a new catalyst or a spent catalyst (a desulfurization catalyst having Ni and Mo supported on alumina used for 11 months in an atmospheric-pressure residue desulfurization process), the total acid value was 4.2 mgKOH / g The organic acid abatement test was carried out for residual oil. As shown in Table 7, it was confirmed that the organic acid reduction performance similar to that of the new catalyst can be obtained even when the spent catalyst is used. Therefore, the activity of reducing the organic acid of the spent catalyst is industrially applicable for the reduction of organic acid.
실시예 3-3: 혼합가스를 사용한 잔사 유분 내의 유기산 저감Example 3-3: Reduction of organic acid in residue oil using a mixed gas
실시예 4: 탄화수소류 유분 내의 성분 변화 검토Example 4: Examination of composition change in hydrocarbon oil fraction
유기산 저감 공정을 거친 후, 탄화수소 유분 시료 중의 질소, 황 성분 함량은 유의적인 변화가 없었으며, 거의 무시 가능한 수준이었다.After the organic acid abatement process, the contents of nitrogen and sulfur in the hydrocarbon oil samples were not significantly changed and were almost negligible.
본 발명은 상기한 실시예에 의하여 한정되는 것이 아니고, 본 발명의 사상 및 범위를 벗어나지 않고 다양하게 수정 및 변형을 할 수 있음은 이 기술 분야에서 통상의 지식을 가진 자에게는 자명하다. 따라서 그러한 수정예 또는 변형예들 역시 본 발명의 특허청구범위에 속하는 것으로 보아야 한다.It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention. It is therefore intended that such modifications or alterations be within the scope of the appended claims.
본 발명은 비교적 낮은 압력 하의 마일드한 조건 하에서 강한 부식 활성을 갖는 유기산을 효과적으로 저감시킬 수 있는 유기산 저감 방법을 제공한다. 본 발명에 따르면, 현재 정유공장에 적용 가능하도록 공정 변수를 적절히 조합함으로써, 보다 경제적이고 마일드한 조건 하에서 고산도 탄화수소류 유분 내의 유기산을 효율적으로 저감시킬 수 있으므로, 산업상 직접 이용가능한 실용적인 공정을 제공한다.The present invention provides an organic acid abatement method capable of effectively reducing an organic acid having a strong corrosive activity under a mild condition under a relatively low pressure. According to the present invention, it is possible to effectively reduce organic acids in high-acidity hydrocarbon fractions under more economical and mild conditions by suitably combining process variables so as to be applicable to refinery plants at present, do.
Claims (17)
Translated fromKorean300℃ 내지 400℃의 온도 및 3 내지 15kg·f/㎠의 압력 하의 수소화 촉매 존재 하에서, 유분 1L 당 1 내지 100NL의 H2의 비로 수소 가스를 공급하여 탄화수소류 유분을 수소화하는 단계를 포함하며, 여기서 상기 수소 가스는 20 내지 80 중량%의 수소를 포함하는 혼합 가스이고, 상기 혼합 가스는 휘발유, 경유 탈황 공정에서 발생하는 수소 혼합 오프-가스이며, 상기 수소화 촉매는 폐촉매이고,
상기 방법은 상기 탄화수소류 유분 내 유기산을 70% 이상 저감시키며, 상기 수소화 단계에서 탄화수소류 유분 중 황 화합물과 질소 화합물의 수소화는 실질적으로 일어나지 않는, 탄화수소류 유분 내의 유기산을 저감하는 방법.As a method for reducing organic acids in hydrocarbon oil fractions,
And hydrogenating the hydrocarbon oil fraction by supplying hydrogen gas at a ratio of 1 to 100 NL H2 / L oil in the presence of a hydrogenation catalyst at a temperature of 300 to 400 ° C and a pressure of 3 to 15 kg · f / cm2 , Wherein the hydrogen gas is a mixed gas containing 20 to 80% by weight of hydrogen, the mixed gas is a hydrogen mixing off-gas generated in a gasoline or gas oil desulfurization process, the hydrogenation catalyst is a spent catalyst,
The method reduces organic acids in hydrocarbon fractions by at least 70% and does not substantially hydrogenate the sulfur compounds and nitrogen compounds in the hydrocarbon fractions in the hydrogenation step.
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| PCT/KR2012/000080WO2012096470A2 (en) | 2011-01-10 | 2012-01-04 | Method for reducing the amount of organic acids in a hydrocarbon oil fraction |
| EP12734329.1AEP2664662B1 (en) | 2011-01-10 | 2012-01-04 | Method for reducing the amount of organic acids in a hydrocarbon oil fraction |
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